Superhydrophobic surfaces with low and high adhesion made from mixed (hydrocarbon and fluorocarbon) 3,4-propylenedioxythiophene monomers

International audienceThis work concerns new superhydrophobic surfaces, generated by replacing long fluorocarbon chains, which bioaccumulate, with short chains whilst at the same time retaining oleophobic properties. Here, is described the synthesis of novel original 3,4-propylenedioxythiophene derivatives containing both a short fluorocarbon chain (perfluorobutyl) and a hydrocarbon chain of various lengths (ethyl, butyl and hexyl). Superhydrophobic (contact angle water > 150° ) surfaces with good oleophobic properties (60° > contact angle hexadecane > 80° ) have been obtained by electrodeposition using cyclic voltammetry. Surprisingly, the lowest hystereses and sliding angles (Lotus effect) are obtained with the shortest alkyl chains due to the presence of microstructures made of nanofibers on the surfaces, whereas, the longest alkyl chains leads to nanosheets with high adhesion (Petal effect). Such materials are potential candidates for biomedical applications

Conception of low surface energy materials : a novel step towards sustainable products

Les matériaux à faible énergie de surface (LSEMs) sont conçus pour différentes applications. Parmi celle-ci, les applications sur un support solide pour l’élaboration de surfaces superhydro/oléophobes ainsi qu’à l'interface de 2 milieux distincts pour la synthèse de nouveaux tensioactifs éco-responsables. Actuellement, ces matériaux sont constitués essentiellement de composés fluorés pour leurs propriétés uniques leur conférant à la fois l’hydro- et oléo-phobie ainsi que pour leur stabilité thermique et chimique dans des milieux corrosifs. Ce projet montre que l’élaboration des surfaces superhydro/oléophobes peut être réalisée sans utiliser nécessairement des chaînes perfluorées. Deux approches sont adoptées dans ce processus. La première stratégie est d'étudier l'influence de la longueur de la chaîne fluorée sur la structuration et la mouillabilité de la surface des dérivés du ProDOT. La seconde est d'explorer l'influence d'une chaine hydrocarbonée incorporée au coeur des monomères et d'étudier l'effet du type et de la longueur de ces chaînes sur les propriétés de surface. Dans le cadre de l'application des LSEMs sur les ‘matériaux mous’, deux études ont été réalisées : la première se focalisant sur l'effet de la longueur des chaînes hydrocarbonées sur les tensioactifs hybrides à courte chaine fluorée et la deuxième étudiant l'effet de la tête polaire. Deux séries de sulfates et bisulfates hybrides ont donc été synthétisées et leurs propriétés physico-chimiques étudiées. Ce travail a abouti à des résultats intéressants.Two types of Low surface energy materials LSEMs can be recognized; those which are firstly applied on solid surfaces to elaborate superhydro/oleophobic surfaces that are micro and nano structured, and secondly at the water/air interface to synthesize new ecofriendly surfactants. LSEMs are essentially made from fluorinated compounds due to their unique properties of being both hydro and oleophobic as well as, their thermal and chemical stability in corrosive media. This project shows that the creation of superhydrophobic materials with high oleophobic properties does not necessarily require the utilization of long and bioaccumulative perfluorocarbon chains. Two approaches were adopted in this field. The first strategy was to develop ProDOT derivatives bearing short fluorinated chains to study the influence of the fluorinated chain length on the surface wettability. The proceeding part was to explore the effect of the introduction of a hydrocarbon tail and study the effect of their type and chain length on the surface properties. Another important aspect of this research involves the application of LSEMs on soft materials like surfactants as alternatives to toxic perfluorinated homologues. This study was done to explore the effect of the variant hydrocarbon chains with a short fluorinated tail of hybrid surfactants as well as the effect of the polar head. In this area, two families of hybrid sulfate and bisulfates were synthesized. Their physico-chemical properties were investigated and interesting results were obtained

Controlling electrodeposited conducting polymer nanostructures with the number and the length of fluorinated chains for adjusting superhydrophobic properties and adhesion

International audienceControlling the formation of surface nanostructures is highly important for various applications, and in particular for superhydrophobic properties. Here, taking 3,4-propylenedioxythiophene (ProDOT) as a model molecule, we study the influence of the decrease in the perfluorocarbon chain length or the use of two shorter perfluorocarbon chains on the formation of surface nanostructures and superhydrophobic by electropolymerization. Moreover, perfluorinated compounds, especially those with long perfluorocarbon chains, are extremely used in industry but the discovery of their persistence, bioaccumulation potential and toxicity alternatives have to be found. Hopefully, it seems that their effect is dependent on the perfluorinated chain length and that alternatives with shorter perfluorinated chains can be envisaged. Here, we show in the fabrication of superhydrophobic surfaces that the use of shorter perfluorocarbon chains can even, in certain conditions, lead to better properties. Superhydrophobic properties with extremely low hysteresis are obtained with long perfluorocarbon chains (C8F17) but very close properties are also obtained with short perfluorobutyl (C4F9) and even perfluoroethyl (C2F5) chains. Superoleophilic properties are obtained with C2F5 chains, whereas the highest oleophobic properties were elaborated with the C4F9 chains. This is due to a change in the surface morphology from cauliflower structures to nanofibers as the perfluorocarbon chain decreases. By contrast, the use of two shorter perfluorocarbon chains induces very high steric hindrance during the electropolymerization and as a consequence smoother surfaces with lower surface hydrophobicity. Hence, it is possible to form structured or smooth surfaces using one or two fluorinated chains, respectively

Universal control of protons concentration using electrochemically generated acid compatible with miniaturization

Controlling locally produced acidity in miniaturized spaces is of high importance yielding to manage simultaneous chemical reactions. Here we present a platform that hosts miniaturized micro reactors, each one enabling electrochemical control of the acidity in ~nL volumes. We demonstrated the local control of chemical reactions with the deprotection of strong acid labile groups in a region of 150 μm of diameter of an upstanding glass using high proton concentrations (~10-1M) and the acidity contrasts between the cell region and the outside. We demonstrated an accurate control of the proton concentration in aqueous and organic solvents and the control of chemical reactions in organic electrolytes achieved with a sulfonated tetrafluoroethylene-based membrane, that isolates the acid generating electrodes from the reagents in the solution. The quantitative control of the acidity by the Faradaic currents was demonstrated by the calibration of carboxyfluorescein adjusted with external titrations, and with a tautomer transition occurring at pH 4.2. To the best of our knowledge, this platform shows the best control of acidity in the smallest volume reported so far

Surfactants with low fluorine content

International audienc

Recent Advances in Metal-Catalyzed Alkyl–Boron (C(sp3)–C(sp2)) Suzuki-Miyaura Cross-Couplings

Boron chemistry has evolved to become one of the most diverse and applied fields in organic synthesis and catalysis. Various valuable reactions such as hydroborylations and Suzuki–Miyaura cross-couplings (SMCs) are now considered as indispensable methods in the synthetic toolbox of researchers in academia and industry. The development of novel sterically- and electronically-demanding C(sp3)–Boron reagents and their subsequent metal-catalyzed cross-couplings attracts strong attention and serves in turn to expedite the wheel of innovative applications of otherwise challenging organic adducts in different fields. This review describes the significant progress in the utilization of classical and novel C(sp3)–B reagents (9-BBN and 9-MeO-9-BBN, trifluoroboronates, alkylboranes, alkylboronic acids, MIDA, etc.) as coupling partners in challenging metal-catalyzed C(sp3)–C(sp2) cross-coupling reactions, such as B-alkyl SMCs after 2001

Functionalized oxide biosensor interfaces for in-situ, acid-modulated peptide synthesis

In this paper we report a novel acid-modulated strategy for peptide microarray production on biosensor interfaces. We have initially selected controlled pore glass (CPG) as support for solid phase peptide synthesis (SPPS) to implement a chemistry that can be efficiently performed at the interface of multiple FET sensors, eventually to generate label-free peptide microarrays for protein screening. Our chemistry uses temporary protection of the N-terminal amino function of each amino acid building block with a tert-butyloxycarbonyl (Boc) group that can be removed after each SPPS cycle, in combination with semi-permanent protection of the side chains of trifunctional amino acid residues. Such protection scheme, with a well-proven record of application in conventional, batchwise SPPS, has been fine tuned for optimal performance on CPG and, from there, translated to SPR chips that allow layer-by-layer monitoring of amino acid coupling. Our results validate this acid-modulated synthesis as a feasible approach for producing peptides in high yield and purity on flat glass surfaces such as those in bio-FETs

Mussel-Inspired Electro-Cross-Linking of Enzymes for the Development of Biosensors

International audienceIn medical diagnosis and environmental monitoring, enzymatic biosensors are widely applied because of their high sensitivity, potential selectivity, and their possibility of miniaturization/automation. Enzyme immobilization is a critical process in the development of this type of biosensors with the necessity to avoid the denaturation of the enzymes and ensuring their accessibility toward the analyte. Electrodeposition of macromolecules is increasingly considered to be the most suitable method for the design of biosensors. Being simple and attractive, it finely controls the immobilization of enzymes on electrode surfaces, usually by entrapment or adsorption, using an electrical stimulus. Performed manually, enzyme immobilization by cross-linking prevents enzyme leaching and was never done using an electrochemical stimulus. In this work, we present a mussel-inspired electro-cross-linking process using glucose oxidase (GOX) and a homobifunctionalized catechol ethylene oxide spacer as a cross-linker in the presence of ferrocene methanol (FC) acting as a mediator of the buildup. Performed in one pot, the process takes place in three steps: (i) electro-oxidation of FC, by the application of cyclic voltammetry, creating a gradient of ferrocenium (FC+); (ii) oxidation of bis-catechol into a bis-quinone molecule by reaction with the electrogenerated FC+; and (iii) a chemical reaction of bis-quinone with free amino moieties of GOX through Michael addition and a Schiff's base condensation reaction. Employed for the design of a second-generation glucose biosensor using ferrocene methanol (FC) as a mediator, this new enzyme immobilization process presents several advantages. The cross-linked enzymatic film (i) is obtained in a one-pot process with nonmodified GOX, (ii) is strongly linked to the metallic electrode surface thanks to catechol moieties, and (iii) presents no leakage issues. The developed GOX/bis-catechol film shows a good response to glucose with a quite wide linear range from 1.0 to 12.5 mM as well as a good sensitivity (0.66 μA/mM cm2) and a high selectivity to glucose. These films would distinguish between healthy (3.8 and 6.5 mM) and hyperglycemic subjects (>7 mM). Finally, we show that this electro-cross-linking process allows the development of miniaturized biosensors through the functionalization of a single electrode out of a microelectrode array. Elegant and versatile, this electro-cross-linking process can also be used for the development of enzymatic biofuel cells

Mussel-Inspired Electro-Cross-Linking of Enzymes for the Development of Biosensors

In medical diagnosis and environmental monitoring, enzymatic biosensors are widely applied because of their high sensitivity, potential selectivity, and their possibility of miniaturization/automation. Enzyme immobilization is a critical process in the development of this type of biosensors with the necessity to avoid the denaturation of the enzymes and ensuring their accessibility toward the analyte. Electrodeposition of macromolecules is increasingly considered to be the most suitable method for the design of biosensors. Being simple and attractive, it finely controls the immobilization of enzymes on electrode surfaces, usually by entrapment or adsorption, using an electrical stimulus. Performed manually, enzyme immobilization by cross-linking prevents enzyme leaching and was never done using an electrochemical stimulus. In this work, we present a mussel-inspired electro-cross-linking process using glucose oxidase (GOX) and a homobifunctionalized catechol ethylene oxide spacer as a cross-linker in the presence of ferrocene methanol (FC) acting as a mediator of the buildup. Performed in one pot, the process takes place in three steps: (i) electro-oxidation of FC, by the application of cyclic voltammetry, creating a gradient of ferrocenium (FC⁺); (ii) oxidation of bis-catechol into a bis-quinone molecule by reaction with the electrogenerated FC⁺; and (iii) a chemical reaction of bis-quinone with free amino moieties of GOX through Michael addition and a Schiff’s base condensation reaction. Employed for the design of a second-generation glucose biosensor using ferrocene methanol (FC) as a mediator, this new enzyme immobilization process presents several advantages. The cross-linked enzymatic film (i) is obtained in a one-pot process with nonmodified GOX, (ii) is strongly linked to the metallic electrode surface thanks to catechol moieties, and (iii) presents no leakage issues. The developed GOX/bis-catechol film shows a good response to glucose with a quite wide linear range from 1.0 to 12.5 mM as well as a good sensitivity (0.66 μA/mM cm²) and a high selectivity to glucose. These films would distinguish between healthy (3.8 and 6.5 mM) and hyperglycemic subjects (>7 mM). Finally, we show that this electro-cross-linking process allows the development of miniaturized biosensors through the functionalization of a single electrode out of a microelectrode array. Elegant and versatile, this electro-cross-linking process can also be used for the development of enzymatic biofuel cells